Extraction of hydrocarbons from hydrocarbon-containing materials

ABSTRACT

A method of extracting hydrocarbon-containing organic matter from a hydrocarbon-containing material includes the steps of providing a first liquid comprising a turpentine liquid; contacting the hydrocarbon-containing material with the turpentine liquid to form an extraction mixture; extracting the hydrocarbon material into the turpentine liquid; and separating the extracted hydrocarbon material from a residual material not extracted.

CROSS REFERENCE TO RELATED APPLICATION(S)

This application is a 35 U.S.C. §371 National Phase Entry Applicationfrom PCT/US2008/010831, filed Sep. 17, 2008, and designating the UnitedStates. This application is also a Continuation-in-part of U.S.application Ser. Nos. 12/174,139, filed Jul. 16, 2008, and 12/053,126,filed Mar. 21, 2008, and claims the benefit of U.S. ProvisionalApplication No. 60/973,964, filed Sep. 20, 2007, each of which isincorporated by reference in their entirety.

FIELD OF THE INVENTION

The present invention relates to the field of extraction of hydrocarbonsfrom hydrocarbon-containing materials.

BACKGROUND OF THE INVENTION

The liquefaction, solubilization and/or extraction of fossil fuels, alsocalled hydrocarbon-containing organic matter, in solid, semi-solid,highly viscous or viscous form (individually and jointly referred to asfossil fuels hereafter) have proven to be extremely challenging anddifficult. As used herein, such fossils fuels include, but are notlimited to, hydrocarbon-containing organic matter within coal, oilshale, tar sands and oil sands (hereinafter jointly called tar sands),as well as crude oil, heavy crude oil, crude bitumen, kerogen, naturalasphalt and/or asphaltene. The difficulty can in part be attributed tothe fact that these fossil fuels include complex organic polymers linkedby oxygen and sulfur bonds, which are often imbedded in the matrices ofinorganic compounds. A need exists to produce additional liquidhydrocarbon feed stock for the manufacture of liquid and gaseous fuelsas well as for the production of various chemicals, pharmaceuticals andengineered materials as the demand and consumption for hydrocarbon basedmaterials increases.

Various technologies or processes have been developed to liquefy,solubilize and/or extract the fossil fuels. None of the prior artliquefaction, solubilization and extraction technologies or processes,however, has proven to be commercially viable on a large scale for alltypes of fossil fuels. This is due to the fact that all of the prior arttechnologies and processes for the liquefaction, solubilization orextraction of hydrocarbons developed to date are expensive to deploy andoperate. Additionally, the prior art processes and technologies for theliquefaction, solubilization and/or extraction of hydrocarbons may bedifficult to scale up, operate and/or control because of one or more ofthe following reasons: (1) operating at an inordinately elevatedpressure; (2) operating at a very high temperature; (3) the need forexpensive processing vessels and equipment that require the externalsupply of hydrogen under extreme conditions; (4) being subjected to amixture, or composition, of two or more reagents, catalysts and/orpromoters, which are frequently highly toxic and are neither renewablenor recyclable; (5) requiring to supply a special form of energy, e.g.,microwave radiation; (6) long process times for partial liquefaction,solubilization or extraction; (7) requiring extraordinarily fineparticles with a size of about 200 mesh (0.074 mm), which is profoundlydifficult and costly to manufacture and handle; and (8) being incapableof recovering and recycling the necessary reagents, catalysts and/orpromoters. Thus, there exists a need to provide additional techniquesand processes for the increased recovery of hydrocarbon materials.

For primary drilling operations, it would be advantageous to employ aprocess that would enhance solubilization and encourage movement ofadditional or trapped hydrocarbon-containing organic matter that couldthen be recovered allowing existing pressure gradients to force thehydrocarbon-containing organic matter through the borehole. Inparticular, it would be useful to solubilize heavier hydrocarbons thatusually remain in the reservoir through primary drilling operations.

For secondary and tertiary or enhanced oil recovery operations, it wouldbe advantageous to employ a process that would enhance solubilization ofoil to recover hydrocarbon-containing organic matter in the reservoir ina manner that is cost effect and that does not damage the reservoir.While effective methods and compositions exist for tertiary operations,current methods suffer due to expense of operations in comparison to thevalue of the produced hydrocarbon-containing organic matter.

SUMMARY OF INVENTION

In accordance with one embodiment of the present invention, a method ofextracting hydrocarbon-containing organic matter from ahydrocarbon-containing material, includes the steps of providing a firstliquid including a turpentine liquid and contacting thehydrocarbon-containing material with the turpentine liquid such that anextraction mixture is formed, as well as residual material. Theextraction mixture contains at least a portion of thehydrocarbon-containing organic matter and the turpentine liquid. Theresidual material includes non-soluble material from thehydrocarbon-containing material. The residual material can also includesa reduced portion of the hydrocarbon-containing organic matter in thecircumstance where all such hydrocarbon-containing material has not beensolubilized by the turpentine liquid and moved into the extractionmixture. The residual material is then separated from the extractionmixture. The extraction mixture is further separated into a firstportion and a second portion. The first portion of the extractionmixture includes a hydrocarbon product stream that includes at least aportion of the hydrocarbon-containing organic matter extracted from thehydrocarbon-containing material. The second portion of the extractionmixture includes at least a portion of the turpentine liquid. In oneembodiment, substantially all of the turpentine liquid is recovered inthe recycle stream.

In another embodiment, substantially all hydrocarbon-containing organicmatter is extracted into the extraction mixture. In such embodiment, theresidual materials are essential oil-free and can be further used ordisposed without impact to the environment.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic for one embodiment of an apparatus for therecovery of hydrocarbons from tar sands.

FIG. 2 is a schematic for one embodiment of an apparatus for therecovery of hydrocarbons from oil shale.

FIG. 3 is a schematic for one embodiment of an apparatus for therecovery of hydrocarbons from coal.

FIG. 4 is a schematic for the enhanced recovery of hydrocarbons from asubsurface reservoir.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the present invention relates to a readily deployedcomposition for the extraction, liquefaction and/or solubilization offossil fuels from coal, oil shale, tar sands and the like, as well asfrom reservoirs.

According to one embodiment, a method is providing including the stepsof liquefying, solubilizing and/or extracting hydrocarbon-containingorganic matter from a hydrocarbon-containing material, such as forexample, coal, oil shale, tar sands, or a reservoir containing heavycrude oil, crude oil, natural gas (which frequently coexists with crudeoils and other said fossil fuels), or a combination thereof.Hydrocarbon-containing organic matter includes, but is not limited to,heavy crude oil, crude oil, natural gas and the like.Hydrocarbon-containing organic matter can be solid, semi-solid, liquid,sludge, viscous liquid, liquid or gaseous form. Other materials that aresuitable hydrocarbon-containing materials for treatment using the methodof this invention include liquid and solids that includehydrocarbon-containing materials as well as a residual material.Exemplary hydrocarbon-containing materials can also include oil tankbottoms, oil pit or pond sludge and slurry mix, discarded foods, manure,sewage sludge or municipal garbage. Liquefying, solubilizing and/orextracting the hydrocarbon-containing organic matter includes the stepof providing a turpentine liquid, contacting the hydrocarbon-containingmaterial with the turpentine liquid so as to extract at least a portionof said hydrocarbon-containing organic matter from saidhydrocarbon-containing material into said turpentine liquid to create anextraction mixture that includes the hydrocarbon-containing organicmatter that has been removed from the hydrocarbon-containing materialand the turpentine liquid, and separating the extracted organic matterin the turpentine liquid from any residual material not extracted.Turpentine liquid can include an amount of terpineol. Naturallyoccurring turpentine liquid includes an amount of terpene. In oneembodiment, the turpentine liquid includes α-terpineol.

In certain embodiments, the ratio of turpentine liquid tohydrocarbon-containing material is greater than or equal to about 1:2and 4:1, in some embodiments greater than or equal to about 1:1, and insome embodiments the ratio can be greater than or equal to 2:1 Inembodiments relating the reservoir recovery, the ratio can be greaterthan or equal to about 3:1, and in other embodiments relating toreservoir recovery the ratio can be greater than or equal to about 4:1.For purpose of application in a reservoir, pore volume is used todetermine an estimated measure of the hydrocarbon-containing material.In other aspects of this invention, such as in the use of tar sands andcoal and oil shale, volume of the hydrocarbon-containing material can bemore directly measured.

In certain embodiments, the minimum organic matter contained in thehydrocarbon-containing material is greater than or equal to about 1% byweight, in other embodiments greater than or equal to about 10% byweight, and in still further embodiments greater than or equal to about14% by weight of the hydrocarbon-containing material.

In one embodiment of the invention, a liquefaction, solubilization orextraction reagent of choice for the hydrocarbon-containing matter is anatural, synthetic or mineral turpentine, which can include α-terpineol,or α-terpineol itself.

In certain embodiments, the liquefaction, solubilization and/orextraction of fossil fuels or hydrocarbon-containing organic matter canbe carried out at a temperature, which is within the range of about 2°C. to about 300° C. In certain embodiments, the organic matter ormaterial is contacted with a turpentine liquid at a temperature of lessthan about 300° C., or less than about 60° C. In other embodiments, theliquefaction, solubilization and/or extraction temperatures can bewithin the range of about 20° C. to about 200° C. The pressure underwhich the liquefaction, solubilization and/or extraction of fossil fuelsis to be carried out may typically be within the range of about 1.0×10⁴Pascals (0.1 atm) to about 5.0×10⁶ Pascals (50.0 atm). In certainembodiments, the process can be conducted at a pressure between about5.0×10⁴ Pascals (0.5 atm) to about 8.0×10⁵ Pascals (8.0 atm). In certainother embodiments, the fossil fuels or hydrocarbon-containing organicmatter to be liquefied, solubilized and/or extracted by immersion in, orcontact with, one or more turpentine liquid can be in the form of a bedof particles, pieces, chunks or blocks of fossil fuels whose sizes arewithin the range of about 0.74 mm to about 10 mm in a liquefaction,solubilization or extraction vessel (reactor hereafter) that containsone or more of the said liquefaction, solubilization and/or extractionreagents. In certain embodiments, the sizes of the particles, pieces,chunks or blocks of fossil fuels are within the range of about 0.149 mm(100 mesh) to about 20 mm. In certain embodiments, the bed of particles,pieces, chunks or blocks of fossil fuels is agitated by passing theliquefaction, solubilization and/or extraction reagent or reagents inthe form of liquid through the bed of particles, pieces, chunks orblocks by boiling the reagent or reagents. In certain embodiments, theduration of liquefaction, solubilization and/or extraction is betweenabout 1 minute to about 90 minutes. The fossil fuels can be partially orfully liquefied, solubilized and/or extracted; the degree ofliquefaction, solubilization and/or extraction can be effected bycontrolling the operating conditions, such as temperature, pressure,intensity of agitation and duration of operation, and/or adjusting thetype, relative amount and concentration of the liquefaction,solubilization or extraction reagent or reagents in the reactor.

The basis of one aspect of the present invention is the unexpecteddiscovery that when about 500 grams of the reagent, α-terpineol, wereadded to about 250 grams of the 60-mesh sample of coal from thePittsburgh seam in Washington County of Pennsylvania in a tray, thereagent's color turned pitch black almost immediately, and remained soafter several hours. This indicated that the color change was not due tothe suspension of the coal particles, but rather was indicative of theextraction of hydrocarbon-containing organic matter from the coal.Subsequently, this 2:1 mixture of α-terpineol and the coal sample wastransferred from the tray to a capped and tightly sealed jar and wasmaintained under the ambient conditions of about 20° C. and slightlyless than about 1.01×10⁵ Pascals (1 atm) for about 25 days. Theconversion, (i.e., the degree of liquefaction), of the coal sample wasdetermined to be about 71 wt. % after filtering, washing with ethanol,drying, and weighing. This 71 wt. % conversion corresponds to nearly allthe solubilizable bitumen (organic matter) present in the coal samplewhose proximate analyses are 2.00 wt. % of as-received moisture, 9.25wt. % of dry ash, 38.63 wt. % of dry volatile matter, and 50.12 wt. % ofdry fixed carbon. A series of subsequent experiments with coal, as wellas oil shale and tar sands under various operating conditions, has shownthat the family of reagents that includes natural and/or syntheticturpentines containing pinenes, and alcohols of pinene, i.e.,terpineols, are inordinately effective in liquefying, solubilizingand/or extracting kerogen (organic matter), bitumen (organic matter)and/or asphaltene (organic matter) in the fossil fuels, including coal,oil shale, tar sands, heavy crude oil and/or crude oil, withoutrequiring the aid of any catalyst or alkaline metals. These reagents,except mineral turpentine that is derived from petroleum, are renewableand “green,” i.e., low in toxicity, and relatively inexpensive, ascompared to all other known liquefaction, solubilization and/orextraction reagents for the fossil fuels, such as tetraline, xylene,anthracene, and various solutions or mixtures of these reagents withother compounds. Even mineral turpentine derived from petroleum,although not renewable, is relatively low in toxicity and isinexpensive. It was also found that any of the said liquefaction,solubilization and/or extraction reagents penetrates or diffuses intothe particles, pieces, blocks or chunks of fossil fuels through theirpores at appreciable rates, thus causing these particles, pieces, chunksor blocks to subsequently release the liquefiable, solubilizable orextractable fraction in them often almost nearly completely even underthe far milder conditions, e.g., ambient temperature and pressure, thanthose required by the recent inventions pertaining to the liquefaction,solubilization and/or extraction of the fossil fuels, such as coal, oilshale, tar sands, crude oil and heavy crude oil.

An aspect of the present invention provides a method of liquefying,solubilizing and/or extracting the fossil fuels orhydrocarbon-containing organic matter from hydrocarbon-containingmaterial, such as coal, oil shale and tar sands, wherein a portion ofsolid or semi-solid fossil fuels is contacted with a turpentine liquidin an extraction mixture, which can be in an absence of an alkali metal,catalyst, hydrogen (H₂) and/or carbon monoxide (CO). While hydrogen andCO can be useful as a mixing agent, one embodiment of the inventionincludes the process and the composition in the absence of hydrogen andCO.

In certain embodiments, the turpentine liquid is selected from naturalturpentine, synthetic turpentine, mineral turpentine, pine oil,α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, polymersthereof, and mixtures thereof. In certain other embodiments, theturpentine liquid is selected from geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In otherembodiments, the turpentine liquid is selected from anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.

According to an aspect, solid or semi-solid fossil fuels or otherhydrocarbon-containing materials, such as coal, oil shale, tar sands andheavy crude oil, or for example oil tank bottoms, oil pit or pondsludge, discarded foods, manure, sewage sludge or municipal garbage, maybe provided in any size that facilitates contact with a turpentineliquid. The fossil fuels or hydrocarbon-containing materials can beprovided as particles, pieces, chunks, or blocks, for example, largefragments or pieces of coal or oil shale. According to a certain aspectof the invention, the fossil fuel or hydrocarbon-containing material isprovided as particles. According to a certain aspect of the invention,the particles of fossil fuel or hydrocarbon-containing materials have anaverage particle size of from about 0.074 mm to about 100 mm. In certainother embodiments, the particles of fossil fuel have an average particlesize from about 0.074 mm to about 25 mm.

According to an aspect of the present invention, a second liquid can beadded to the turpentine liquid. According to a certain aspect of theinvention, the second liquid can be selected from lower aliphaticalcohols, alkanes, aromatics, aliphatic amines, aromatic amines, carbonbisulfide and mixtures thereof. Exemplary mixtures include solventsmanufactured in petroleum refining, such as decant oil, light cycle oiland naphtha, or solvents manufactured in dry distilling coal andfractionating liquefied coal.

As used herein, lower aliphatic alcohols refers to primary, secondaryand tertiary monohydric and polyhydric alcohols of between 2 and 12carbon atoms. As used herein, alkanes refers to straight chain andbranched chain alkanes of between 5 and 22 carbon atoms. As used herein,aromatics refers to monocyclic, heterocyclic and polycyclic compounds.As used herein, aliphatic amines refers to primary, secondary andtertiary amines having alkyl substituents of between 1 and 15 carbonatoms. In certain embodiments, benzene, naphthalene, toluene orcombinations thereof are used. In another embodiment, the loweraliphatic alcohols noted above can be used. In one embodiment thesolvent is selected from ethanol, propanol, isopropanol, butanol,pentane, heptane, hexane, benzene, toluene, xylene, naphthalene,anthracene, tetraline, triethylamine, aniline, carbon bisulfide, andmixtures thereof, at a temperature and pressure operable to maintain thesolvent in liquid form.

In certain embodiments, the ratio of turpentine liquid to any otherturpentine-miscible solvent contained in said fluid is greater than orequal to 1:1, in certain embodiments greater than or equal to about 9:4.In certain embodiments, the ratio is greater than or equal to about 3:1.In yet other embodiments, the ratio is greater than or equal to 4:1.

According to an aspect of the present invention, the fossil fuel and theturpentine liquid are contacted at a temperature of from about 2° C. toabout 300° C. In certain embodiments, the fossil fuel is contacted bythe turpentine liquid at a temperature of less than about 200° C.

According to a further aspect of the present invention, the fossil fueland the turpentine liquid are contacted at a pressure of from about1.0×10⁴ Pascals (0.1 atm) to about 5.0×10⁶ Pascals (50 atm). Accordingto an aspect, the method is executed at a pressure of from about 0.5 atmto about 8 atm.

According to an aspect of the present invention, the method furtherincludes providing an extraction vessel within which the solid orsemi-solid fossil fuel is contacted with the turpentine liquid.According to an aspect, agitation means can be provided whereby thefossil fuel and the turpentine liquid contained within the reactor orextractor vessel are mixed and agitated.

According to an aspect of the present invention, the fossil fuel andturpentine liquid can be incubated in a holding tank so as to prolongtheir time of contact. According to a further aspect, the degree ofliquefaction, solubilization and/or extraction is controlled by thelength of time the solid or semi-solid fossil fuel is in contact withthe turpentine liquid and/or the temperature of the mixture of thefossil fuel and turpentine liquid.

According to an aspect of the present invention, the fossil fuel iscontacted with a heterogeneous liquid including a turpentine liquid andwater as an agitant.

In certain embodiments, the ratio of turpentine fluid to water isgreater than or equal to about 1:1 by volume, to avoid slurry formation,which may render separation of the extracted organic matter in theturpentine liquid-containing fluid difficult.

According to an aspect of the present invention, the fossil fuel iscontacted by the turpentine liquid in the presence of an energy inputselected from thermal energy in excess of about 300° C., pressure inexcess of 50 atm, microwave energy, ultrasonic energy, ionizingradiation energy, mechanical shear-forces, and mixtures thereof.

According to an aspect of the present invention, a liquefaction orsolubilization catalyst is provided to the mixture of fossil fuel andturpentine liquid.

According to an aspect of the present invention, the reaction orsolubilization mixture is supplemented by the addition of a compoundselected from hydrogen, carbon monoxide, water, metal oxides, metals,and mixtures thereof.

According to an aspect of the present invention, a microorganism isincluded in the reaction or solubilization mixture. Select chemicalbonds, for example, sulfur cross-links and oxygen cross-links, in thehydrocarbons of fossil fuels and other hydrocarbon-containing materialsare broken by biotreatment with bacillus-type thermophilic andchemolithotrophic microorganisms selected from naturally occurringisolates derived from hot sulfur springs. The breaking of these selectchemical bonds facilitates the solubilization of hydrocarbons in fossilfuels and other hydrocarbon-containing materials.

Still other aspects and advantages of the present invention, it willbecome easily apparent by those skilled in the art from thisdescription, wherein it is shown and described certain embodiments ofthe invention, simply by way of illustration of the best modecontemplated of carrying out the invention. As will be realized, theinvention is capable of other and different embodiments, and its severaldetails are capable of modifications in various obvious respects,without departing from the invention. Accordingly, the description is tobe regarded as illustrative in nature and not as restrictive.

In accordance with one embodiment of the present invention, a method isprovided for extracting hydrocarbon-containing organic matter from ahydrocarbon-containing material comprising a viscous liquid, liquid orgaseous fossil fuel material. The method provides a first liquid thatincludes a turpentine liquid. The turpentine liquid is contacted withthe hydrocarbon-containing material in-situ in an underground formationcontaining said fossil fuel material, thereby forming an extractionmixture so as to extract hydrocarbon-containing organic matter into saidturpentine liquid and form an extraction liquid. The extraction liquidis removed from said formation, wherein the extraction liquid includesthe turpentine liquid containing the extracted hydrocarbon-containingorganic matter. The extracted hydrocarbon-containing organic matter isseparated from a residual material not extracted. The method can furtherinclude separating said extracted hydrocarbon material from theturpentine liquid. The viscous liquid, liquid or gaseous fossil fuelmaterial can be heavy crude oil, crude oil, natural gas, or acombination thereof. The underground formation may be a crude oilreservoir or a natural gas reservoir, for example.

The present invention can be deployed readily in-situ to liquefy and/orsolubilize directly the fossil fuels in underground formations, andextract the resulting liquid products from such formations.

An extraction reagent of the present invention is a liquid, which has avery strong physio-chemical affinity with bituminous organic matter,including bitumen, kerogen and/or tar, in solid coal, oil shale and tarsands. When the extraction reagent of the present invention andbituminous organic matter comprising mainly hydrocarbons come intodirect contact with each other, the organic matter dissolves into theextraction reagent of the present invention, thereby liquefying theorganic matters. Upon contact, the hydrocarbons and the extractionreagent of the present invention rapidly form a homogeneous solution,i.e., a one-phase liquid.

It is possible to take advantage of the physico-chemical affinitybetween the extraction reagent of the present invention and thebituminous matter for enhancing oil recovery from oil reservoirs underin-situ conditions. The prior art in-situ recovery techniques appliedto-date in oil reservoirs resort mostly to the so-called frontaldisplacement method. This process is strictly controlled by thecharacteristics of the multi-phase fluid flow in a porous medium. Thistends to leave a large portion, often exceeding about 40% of theoriginal oil, unrecovered, even for the “good” low viscosity oilreservoirs. The extraction reagent of the present invention enhances oilrecovery by overcoming the complex behavior of the multi-phase flowprevailing under in-situ conditions.

The present invention takes advantage of the very strongphysico-chemical affinity of the turpentine liquid.

One method of the present invention injects an extraction reagent of thepresent invention into an oil or natural gas reservoir through aninjection well.

Oil is dissolved into the extraction reagent of the present inventionwhen the two come into contact in an oil reservoir, thereby yielding ahomogeneous solution, i.e., a one-phase liquid. The extraction reagentof the present invention does not simply displace the oil as it travelsfrom the injection well to the producer well; dissolution of previouslytrapped oil into the extraction reagent of the present inventioncontinues until the extraction reagent is fully saturated with oil.Thereafter, the extraction reagent becomes inactive in the additionaloil recovery process and simply flows through the pores of the reservoiras a one-phase liquid, eventually reaching a production well.

The following illustrates three specific embodiments of in-situ methodsfor oil recovery of the present invention.

In a first in-situ embodiment, about three (3.0) to seven (7.0) porevolumes of an extraction reagent of the present invention are injectedinto an oil reservoir already water-flooded to the residual oilsaturation while producing about 51% of the original oil in thereservoir. The injection of the extraction reagent can unexpectedlyproduce about an additional 41% of the original oil in the reservoir.This embodiment of the method was experimentally validated, as describedin Example 22 herein below.

In a second in-situ embodiment, about two (2.0) to five (5.0) porevolumes of an extraction reagent of the present invention are injectedinto an oil reservoir. At the outset, the injection causes only oil tobe produced until about one-third (0.3) to three-quarter (0.75) of porevolume of the extraction reagent of the present invention is injected;thereafter, the extraction reagent of the present invention in which oilis dissolved, is produced. The majority of the oil present can berecovered upon injecting between about one and a half (1.5) to three anda half (3.5) pore volumes of the reagent. The method unexpectedlyrecovers about 90% of the original oil in the reservoir. This embodimentof the method also is experimentally validated, as described in Example22 herein below.

In a third in-situ embodiment, an extraction reagent of the presentinvention is injected to improve the oil recover from oil reservoirscontaining very viscous oil, e.g., the reservoirs of the “Orinoco OilBelt” in Venezuela. The recovery factor with prior art recovery methodsis low, ranging from 10% to 15% of the original oil in such reservoirs.The unexpected increase in the recovery efficiency from these reservoirswith injection of the turpentine liquid extraction reagent of thepresent invention can be further enhanced by adopting horizontal wellsfor both producers and injectors, and periodic steam soaking of thesewells.

Ultimate recovery of natural gas from a large gas reservoir can beincreased with the injection of an extraction reagent of the presentinvention into a reservoir. The gas production form such a reservoiroften creates dangerously large-scale subsidence on the surfaces of thegas field, e.g., the “Groeningen” field in the Netherlands. As such, itis necessary that the reservoir pressure be maintained by waterinjection. The water injected into the reservoir traps about 30% of thegas in-situ at high pressure due to the two-phase flow of water and gasthrough the reservoir with a low permeability. With the injection of anextraction reagent of the present invention, the trapped gas in thereservoir is dissolved in the reagent and flows to the producer wells.By separating the reagent and gas at the surface, the gas is recoveredand the reagent is recycled for reuse.

The extraction methods of the present invention can be implemented afterone or more of the known methods for facilitating oil production, e.g.,CO₂ or natural gas injection and surfactant addition, are executed.

Exemplary Embodiments for Carrying Out the Invention

Coal

In certain embodiments, anthracite or bituminous coal can be ground tosizes ranging from about 0.841 mm (20 mesh) to about 0.149 mm (100mesh), and subsequently be solubilized and/or extracted, i.e.,liquefied, by immersing in a turpentine liquid under a pressure withinthe range of about 1.0×10⁵ Pascals (1 atm) to about 2.0×10⁵ Pascals (2.0atm). In certain other embodiments, the turpentine liquid can benatural, synthetic or mineral turpentine that includes up to about 50-70volume % of α-terpineol, about 20-40 volume % of β-terpineol, and about10 volume % of other components. In certain embodiments, the bed ofground anthracite or bituminous coal can be agitated by passing saidturpentine liquid at a temperature in the range between 80° C. and about130° C., or possibly up to the boiling point of said turpentine liquid.In certain other embodiments, the duration of solubilization and/orextraction, i.e., liquefaction, can be within about 10 minutes to about40 minutes. In certain embodiments, the contact time for the extractionof hydrocarbon-containing organic matter from coal is less than 5minutes.

In some embodiments, lignite, brown coal, or any other low-rank coalscan be ground to sizes ranging from about 0.419 mm (40 mesh) to about0.074 mm (200 mesh), and subsequently be solubilized and/or extracted,i.e., liquefied, by immersing in a turpentine liquid under a pressurewithin the range of about 1.0×10⁵ Pascals (1 atm) to about 2.0×10⁵Pascals (2.0 atm). In certain other embodiments, the turpentine liquidcan be natural, synthetic or mineral turpentine that includes about70-90 volume % of α-terpineol, about 5-25 volume % of β-terpineol, andabout 5 volume % of other components. In other embodiments, the bed ofground lignite, brown coal, or any other low-rank coals can be agitatedby passing said turpentine liquid at a temperature in the range betweenabout 80° C. and about 130° C., or possibly up to the boiling point ofsaid turpentine liquid. In certain other embodiments, the solubilizationand/or extraction, i.e., liquefaction, can be within about 20 minutes toabout 60 minutes. In certain embodiments, the contact time for theextraction of hydrocarbon-containing organic matter from coal is lessthan 5 minutes.

Oil Shale

In certain embodiments, oil shale can be ground to sizes ranging fromabout 0.419 mm (40 mesh) to 0.074 mm (200 mesh), and subsequently besolubilized and/or extracted, i.e., liquefied, by immersing in aturpentine liquid under a pressure within the range of about 1.0×1.0⁵Pascals (1 atm) to about 2.0×10⁵ Pascals (2.0 atm). In otherembodiments, the turpentine liquid can be natural, synthetic or mineralturpentine that includes about 70-90 volume % of α-terpineol, about 5-25volume % of β-terpineol, and about 5 volume % of other components. Incertain other embodiments, the bed ground oil shale can be agitated bypassing said turpentine liquid at a temperature in the range betweenabout 80° C. and about 130° C., or possibly up to the boiling point ofsaid turpentine liquid. In other embodiments, the solubilization and/orextraction, i.e., liquefaction, can be within about 30 minutes to about60 minutes. In certain embodiments, the contact time for the extractionof hydrocarbon-containing organic matter from oil shale is less than 5minutes.

Tar Sands

In certain embodiments, tar sands can be broken up to sizes ranging fromabout 25.4 mm (1 mesh) to 4.76 mm (4 mesh), and subsequently besolubilized and/or extracted, i.e., liquefied, by immersing in aturpentine liquid under a pressure within the range of about 1.0×1.0⁵Pascals (1 atm) to about 2.0×10⁵ Pascals (2.0 atm). In otherembodiments, the turpentine liquid can be natural, synthetic or mineralthat includes containing about 40-60 volume % of α-terpineol, about30-50 volume % of β-terpineol, 5 volume % of a and/or β-pinene and about5 volume % of other components. In another embodiment, a ground oilshale bed can be agitated by passing said turpentine liquid at atemperature in the range between about 60° C. and about 90° C., orpossibly up to the boiling point of said turpentine liquid. In otherembodiments, the solubilization and/or extraction, i.e., liquefaction,can be within about 10 minutes to about 30 minutes. In certainembodiments, the contact time for the extraction ofhydrocarbon-containing organic matter from tar sands is less than 5minutes.

Crude Oil

In certain embodiments, light and medium crude oil can be produced insitu, i.e., removed from an underground reservoir, for primary,secondary or tertiary recovery, by injecting about one (1.0) to aboutfive (5.0) pore volumes of a turpentine liquid. In other embodiments,between about two (2.0) and about four (4.0) pore volumes of aturpentine liquid can be injected. In certain embodiments, theturpentine liquid can be natural, synthetic or mineral turpentine thatincludes about 40-70 volume % of α-terpineol, about 30-40 volume % of3-terpineol, 10 volume % of a and/or β-pinene and about 10 volume % ofother components. In certain embodiments, the injection of a turpentineliquid can be followed by waterflooding with about one (1.0) to aboutthree (3.0) pore volumes of water.

In certain embodiments, heavy and extra heavy crude oil can be producedin situ, i.e., removed from an underground reservoir, for primary,secondary or tertiary recovery, by injecting about one (1.0) to aboutfive (5.0) pore volumes of a turpentine liquid. In other embodiments,between about two (2.0) and about four (4.0) pore volumes of aturpentine liquid can be injected. In certain embodiments, theturpentine liquid can be natural, synthetic or mineral turpentine thatincludes about 50-70 volume % of α-terpineol, about 20-35 volume % of3-terpineol, 10 volume % of a and/or β-pinene and about 5 volume % ofother components can be used in conjunction with steam injection.

Referring to FIG. 1, an apparatus for the recovery ofhydrocarbon-containing organic matter from tar sands is provided.Apparatus 100 includes turpentine liquid supply 102, which canoptionally be coupled to a pump 104, to supply a turpentine liquid tocontacting vessel or extraction vessel 110. In certain embodiments, theturpentine liquid supply can include means for heating the turpentineliquid. In certain embodiments, the contacting vessel can be an inclinedrotary filter or trommel. Tar sand sample 106 is provided to conveyor108 or like feeding apparatus for supplying the tar sands to an inlet ofcontacting vessel 110. Optionally, conveyor 108 can include a filterscreen or like separating apparatus to prevent large particles frombeing introduced into the process. Contacting vessel 110 includes atleast one inlet 112 for turpentine liquid to be introduced and contactedwith the tar sands. Contacting vessel 110 can include a plurality oftrays or fins 114 designed to retain the tar sands in the contactingvessel for a specified amount of time, and to increase or controlcontact between the tar sand particles and the turpentine liquid. Incertain embodiments, the contacting vessel can be an inclined rotaryfilter. An extraction mixture that includes the extracting liquid andhydrocarbon-containing organic matter extracted from the tar sands isremoved from contacting vessel 110 via outlet 116, which can includefilter 118 to prevent the removal of solids with the extraction mixturethat includes the extracted hydrocarbon-containing organic matter. Pump120 can be coupled to outlet 116 to assist with supplying the extractionmixture to holding tank 122. Line 124 can be coupled to holding tank 122for supplying the extraction mixture for further processing. Afterextraction of the hydrocarbon-containing organic matter, inorganicsolids and other materials not soluble in the turpentine liquid can beremoved from the contacting vessel via second conveyor 126. Someturpentine liquids include, but are not limited to, liquids that includeα-terpineol and β-terpineol.

Referring now to FIG. 2, apparatus 200 is provided for the recovery ofhydrocarbon-containing organic matter from oil shale and othersedimentary rock formations that include recoverable hydrocarbonmaterials. Oil shale sample 202 is supplied to grinder or crusher 204 toreduce the size of the oil shale. Preferably, grinder or crusher 204reduces the oil shale to between about 0.074 and 0.42 mm in diameter.Crushed oil shale may optionally be supplied to a filter to ensureuniform and/or conforming particle size. First conveyor 206 providesparticles from grinder or crusher 204 to contacting vessel 208.Contacting vessel 208 is coupled to turpentine liquid supply 210, whichmay optionally be coupled to a pump, and which supplies a turpentineliquid to at least one inlet 212 coupled to contacting vessel 208. Incertain embodiments, the turpentine liquid supply can include means forheating the turpentine liquid. Contacting vessel 208 can include aplurality of trays or fins 214 designed to retain the tar sands in thecontacting vessel for a specified amount of time, and to increase orcontrol contact between the tar sand particles and the turpentineliquid. In certain embodiments, the contacting vessel can be an inclinedrotary filter or trommel. An extraction mixture stream that includes theturpentine liquid and recovered hydrocarbon-containing organic matterfrom the oil shale is collected via outlet 216 and supplied to holdingtank 220. Pump 218 is optionally coupled to outlet 216 to assist withthe supply of the extraction mixture stream to holding tank 220. Theextraction mixture stream can be coupled to line 222 for supplying theextraction mixture stream to further processing. Second conveyor 224assists with the removal of inorganic or insoluble materials fromcontacting vessel 208. Turpentine liquids can include, but are notlimited to, α-terpineol and β-terpineol.

Referring now to FIG. 3, apparatus 300 is provided for the recovery ofhydrocarbon-containing organic matter from coal. Coal sample 302 issupplied to grinder or crusher 304 to reduce the size of the coal.Preferably, grinder or crusher 304 reduces the coal to between about0.074 and 0.84 mm in diameter, depending upon the quality of the coalsample. In certain embodiments, the grinder or crusher 304 can be a wetgrinder. Crushed coal may optionally be supplied to a filter to ensureuniform and/or conforming particle size. Crushed coal is supplied tofirst contacting vessel 306. First contacting vessel 306 is also coupledto a turpentine liquid supply 308, which may optionally be coupled topump 310, and which supplies the turpentine liquid to first contactingvessel 306. In certain embodiments, the turpentine liquid supply caninclude means for heating the turpentine liquid. First contacting vessel306 includes mixing means 312 designed to agitate and improve or controlcontact between the solid coal particles and the turpentine liquid. Anextraction mixture stream that includes the turpentine liquid andrecovered hydrocarbon-containing organic matter from the oil shale iscollected via first contacting vessel outlet 313 and supplied to secondcontacting vessel 316. Pump 314 is optionally coupled to outlet 313 toassist with the supply of the extraction mixture stream to the secondcontacting vessel 316. Second contacting vessel 316 can include a seriesof trays or fins 318 designed to increase or control separation of thesolids and turpentine liquids. Optionally, the second contacting vessel316 can be an inclined rotary filter or trommel. The extraction mixturestream can be collected from second contacting vessel outlet 320, whichmay optionally be coupled to pump 322, to assist with supply of theextraction mixture stream to holding tank 324. Liquid coal and anyturpentine liquid present in holding tank 324 can be supplied to aliquid coal refinery or other processing step via line 326. Conveyor 328can be coupled to second contacting vessel 316 for removal and recoveryof the solids as a by-product of the process. Turpentine liquids caninclude, but are not limited to, α-terpineol and β-terpineol. Theapparatus 300 can also be used to process high and low grade oil shale.

Referring now to FIG. 4, process 400 is provided for the enhancedrecovery of hydrocarbon-containing organic matter from ahydrocarbon-containing subsurface formation. Hydrocarbon-containingreservoir 404 is shown positioned below the surface 402. Production well406 is already in operation. Injection well 408 is provided for theinjection of a turpentine liquid via line 410. The turpentine liquidfacilitates the liquefaction, solubilization and/or extraction ofhydrocarbon-containing organic matter present in the reservoir, as wellas providing the driving force to push the hydrocarbon-containingorganic matter in the formation toward the production well. Ahydrocarbon product stream that includes injected turpentine liquid iscollected via line 412. Turpentine liquids can include, but are notlimited to, α-terpineol and β-terpineol.

In certain embodiments, the turpentine liquid for increasing productionfrom an oil well is provided that includes at least 30% by volume ofnatural turpentine, synthetic turpentine, mineral turpentine, pine oil,α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpeneresins, α-terpene, β-terpene, γ-terpene, or mixtures thereof. In otherembodiments, the turpentine liquid includes at least 30% by volumegeraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane,2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,isoborneol, p-menthan-8-ol, α-terpinyl acetate, citronellol,p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, ormixtures thereof. In yet other embodiments, the turpentine liquidincludes at least 30% by volume anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, or mixtures thereof.

In certain embodiments, the turpentine liquid includes at least about40% by volume α-terpineol. In other embodiments, the turpentine liquidincludes at least about 25% by volume β-terpineol. In yet otherembodiments, the turpentine liquid includes at least about 40% by volumeα-terpineol and at least about 25% by volume β-terpineol. In otherembodiments, the turpentine liquid includes at least about 50%α-terpineol, and in certain embodiments also includes 13 terpineol. Incertain embodiments, the turpentine liquid includes at least 20% byvolume of β-terpineol. In certain embodiments, the turpentine liquidincludes between about 50 and 70% by volume of α-terpineol and betweenabout 10 and 40% by volume of β-terpineol.

In another aspect, a process for increasing production from asub-surface hydrocarbon-containing reservoir undergoing enhancedrecovery operations is provided that includes injecting a turpentineliquid into the reservoir through an injection well to stimulateproduction of the hydrocarbon-containing material. The turpentine liquidcan include at least one compound selected from natural turpentine,synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene,α-terpineol, β-terpineol, γ-terpineol, terpene resins, α-terpene,β-terpene, γ-terpene, and mixtures thereof. In other embodiments, theturpentine liquid can include at least one compound selected fromgeraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane,2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,isoborneol, p-menthan-8-ol, α-terpinyl acetate, citronellol,p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, andmixtures thereof. In yet other embodiments, the turpentine liquid caninclude at least one compound selected from anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof. A hydrocarbon-containing organic matterproduction stream that includes the turpentine liquid and recoveredhydrocarbons is recovered from the production well associated with thehydrocarbon-containing reservoir. The hydrocarbon-containing organicmatter production stream can be separated into a recovered hydrocarbonsstream and a turpentine liquid recycle stream. In certain embodiments,the method of further can further include the step of injecting theturpentine liquid recycle stream into the injection well.

In another aspect, a method for the increasing production from ahydrocarbon-containing sub-surface hydrocarbon formation undergoingenhanced recovery operations is provided. The method includes the stepsof injecting a turpentine liquid into the formation through an injectionwell. In certain embodiments, the turpentine liquid includes at least40% by volume α-terpineol and at least 10% by volume β-terpineol. Theturpentine liquid solubilizes, extracts and/or displaces thehydrocarbon-containing materials from the formation, which aresubsequently recovered from the formation with the turpentine liquidthrough a production well. In certain embodiments, the method furtherincludes separating the hydrocarbons from the turpentine liquid. In yetother embodiments, the method further includes recycling the turpentineliquid to the injection well. In certain embodiments, α-terpineol ispresent in an amount between about 40 and 70% by volume. In certainother embodiments, α-terpineol is present in an amount of at least 70%by volume. In yet other embodiments, β-terpineol is present in an amountbetween about 10 and 40% by volume. In other embodiments, the turpentineliquid further includes up to about 10% by volume γ-terpineol. In otherembodiments, the turpentine liquid can include up to about 25% by volumeof an organic solvent selected from methanol, ethanol, propanol, tolueneand xylenes. The method is useful for the recovery ofhydrocarbon-containing organic matter during primary, secondary andtertiary recovery operations, including after secondary recoveryoperations that include waterflooding.

In another aspect, a turpentine liquid for the recovery ofhydrocarbon-containing organic matter from tar sands is provided. In oneembodiment, the turpentine liquid includes at least about 30% by volumeα-terpineol and at least about 25% by volume β-terpineol. In anotherembodiment, the turpentine liquid includes between about 30 and 70% byvolume α-terpineol, between about 25 and 55% by volume β-terpineol, upto about 10% by volume α-terpene, and up to about 10% by volumeβ-terpene.

In another aspect, a turpentine liquid for recoveringhydrocarbon-containing organic matter from high grade coal sources, suchas for example, anthracite or bituminous coal, is provided. In oneembodiment, the turpentine liquid includes at least about 45% by volumeα-terpineol and at least about 15% by volume β-terpineol. In anotherembodiment, the turpentine liquid includes between about 45 and 80% byvolume α-terpineol, between about 15 and 45% by volume β-terpineol, upto about 10% by volume α-terpene, and up to about 10% by volumeβ-terpene.

In another aspect, a turpentine liquid for recoveringhydrocarbon-containing organic matter from low grade coal sources isprovided. In one embodiment, the turpentine liquid includes at leastabout 60% by volume α-terpineol and up to about 30% by volumeβ-terpineol. In another embodiment, the turpentine liquid includesbetween about 60 and 95% by volume α-terpineol, up to about 30% byvolume β-terpineol, up to about 5% by volume α-terpene, and up to about5% by volume β-terpene.

In another aspect, a turpentine liquid for recoveringhydrocarbon-containing organic matter from oil shale is provided. Asused herein, oil shale generally refers to any sedimentary rock thatcontains bituminous materials. In one embodiment, the turpentine liquidincludes at least about 60% by volume α-terpineol and up to about 30% byvolume β-terpineol. In another embodiment, the turpentine liquidincludes between about 60 and 95% by volume α-terpineol, up to about 30%by volume β-terpineol, up to about 5% by volume α-terpene, and up toabout 5% by volume 3-terpene.

In another aspect, a turpentine liquid is provided for recoveringhydrocarbon-containing organic matter from light and medium crude oil.In one embodiment, the turpentine liquid includes at least about 40 and70% by volume α-terpineol and at least about 30 and 40% by volumeβ-terpineol. In yet another embodiment, the turpentine liquid includesbetween about 40 and 70% by volume α-terpineol, between about 30 and 40%by volume β-terpineol, up to about 10% by volume α-terpene, and up toabout 10% by volume β-terpene.

In another aspect, a turpentine liquid is provided for recoveringhydrocarbon-containing organic matter from heavy and extra heavy crudeoil. In one embodiment, the turpentine liquid includes at least about 50and 70% by volume α-terpineol and at least about 30 and 40% by volumeβ-terpineol. In another embodiment, the turpentine liquid includesbetween about 50 and 70% by volume α-terpineol, between about 30 and 40%by volume β-terpineol, up to about 10% by volume α-terpene, and up toabout 10% by volume β-terpene.

In another aspect, a method for recovering hydrocarbon-containingorganic matter from tar sands is provided. The method includes mining aformation rich in tar sands to provide a tar sand sample, wherein thetar sand sample includes a recoverable hydrocarbon-containing organicmatter and residual inorganic or insoluble material. The tar sand sampleis supplied to a contacting vessel, wherein the contacting vesselincludes at least one inlet for supplying a turpentine liquid forrecovery of hydrocarbons from the tar sands. The tar sand sample iscontacted with a turpentine liquid to extract the hydrocarbon-containingorganic matter from the tar sands to produce a residual material and anextraction mixture. The extraction mixture includes the turpentineliquid and recovered hydrocarbon-containing organic matter, and theresidual material is separated from the turpentine liquid to producehydrocarbon product stream and a turpentine liquid recycle stream. Incertain embodiments, the method further includes the step of recyclingthe turpentine liquid recycle stream to the contracting vessel. In otherembodiments, the extraction mixture can be separated by distillation toproduce the hydrocarbon product stream and the turpentine liquid recyclestream.

In certain embodiments, the turpentine liquid can include α-terpineol.In other embodiments, the turpentine liquid can include at least about40% by volume α-terpineol and between 10 and 40% by weight β-terpineol.In certain embodiments, between 0.5 and 4 equivalents of the turpentineliquid is used to contact the tar sands and recover hydrocarbons. Incertain embodiments, between 0.5 and 2.0 equivalents of the turpentineliquid is used to contact the tar sands and recover hydrocarbons.

In another aspect, a method for recovering hydrocarbon-containingorganic matter from a hydrocarbon rich oil shale is provided. The methodincludes mining a rock formation that includes hydrocarbon-containingorganic matter to produce a hydrocarbon containing oil shale thatincludes a recoverable hydrocarbon material and inorganic or insolublematerial. The oil shale is ground to produce crushedhydrocarbon-containing oil shale. The crushed hydrocarbon-containing oilshale is then filtered with a filter screen to prevent or control theexcessively large particles from being supplied to the extractionprocess. The crushed hydrocarbon-containing oil shale is fed to acontacting vessel, wherein the contacting vessel includes at least oneinlet for supplying a turpentine liquid for recovery of hydrocarbonsfrom the crushed hydrocarbon-containing oil shale. The crushedhydrocarbon-containing oil shale is contacted with the turpentine liquidto extract the hydrocarbon-containing organic matter from the crushedhydrocarbon-containing oil shale to produce inorganic solids and anextraction mixture that includes the turpentine liquid and recoveredhydrocarbons. The inorganic or insoluble materials are removed from theextraction mixture, and the recovered hydrocarbons are separated fromthe turpentine liquid to produce a hydrocarbon product stream and aturpentine liquid recycle stream. In certain embodiments, the turpentineliquid recycle stream is recycled to the contracting vessel. In otherembodiments, the crushed hydrocarbon-containing oil shale has a meanparticle size of less than about 0.42 mm in diameter. In otherembodiments of the method for the recovery of hydrocarbon-containingorganic matter from oil shale, the turpentine liquid includes at leastone compound selected from natural turpentine, synthetic turpentine,mineral turpentine, pine oil, α-pinene, β-pinene, α-terpineol,β-terpineol, γ-terpineol, terpene resins, α-terpene, β-terpene,γ-terpene, or mixtures thereof. In other embodiments, the turpentineliquid includes at least one compound selected from geraniol, 3-carene,dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide,terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In otherembodiments, the turpentine liquid includes at least one compoundselected from anethole, camphene; p-cymene, anisaldeyde,3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene, alloocimene,alloocimene alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor,citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid,cintronellal, menthone, and mixtures thereof. In certain embodiments,the turpentine liquid can include α-terpineol. In other embodiments, theturpentine liquid can include at least about 40% by volume α-terpineoland between 10 and 40% by weight β-terpineol. In certain embodiments,between 0.5 and 4 equivalents of the turpentine liquid is used tocontact the oil shale and recover hydrocarbon-containing organic matter.In certain embodiments, between 0.5 and 2.0 equivalents of theturpentine liquid is used to contact the oil shale and recoverhydrocarbons.

In another aspect, a method for recovering hydrocarbon-containingorganic matter from a coal rich sub-surface formation is provided. Themethod includes mining the sub-surface formation to produce coal,wherein the coal includes a recoverable hydrocarbon-containing organicmatter and inorganic or insoluble material. The coal is ground toproduce crushed coal and filtered to provide a sample of uniform ordesired size. The crushed coal is fed to a contacting vessel, whereinthe contacting vessel includes at least one inlet for supplying aturpentine liquid for recovery of hydrocarbons from crushed coal, andcontacted with the turpentine liquid to extract the hydrocarbons fromthe crushed coal to produce inorganic solids and an extraction mixture.The extraction mixture includes the turpentine liquid and recoveredhydrocarbons. The inorganic or insoluble solids are separated from theextraction mixture, and the recovered hydrocarbons are separated fromthe turpentine liquid to produce a liquid coal product stream and aturpentine liquid recycle stream. In certain embodiments, the methodfurther includes recycling the turpentine liquid recycle stream to thecontracting vessel. In yet other embodiments, the liquid coal productstream is supplied to a liquid coal refinery. In certain embodiments,the coal sample includes a low grade coal having a mean particle size ofless than about 0.42 mm. In certain embodiments, the coal sampleincludes a high grade coal having a mean particle size of less thanabout 0.84 mm.

In yet other embodiments of the method for recoveringhydrocarbon-containing organic matter from coal, the turpentine liquidincludes at least one compound selected from natural turpentine,synthetic turpentine, mineral turpentine, pine oil, α-pinene, β-pinene,α-terpineol, β-terpineol, γ-terpineol, terpene resins, α-terpene,β-terpene, γ-terpene, or mixtures thereof. In other embodiments, theturpentine liquid includes at least one compound selected from geraniol,3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinanehydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol,p-menthan-8-ol, α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In otherembodiments, the turpentine liquid includes at least one compoundselected from anethole, camphene; p-cymene, anisaldeyde,3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene, alloocimene,alloocimene alcohols, 2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor,citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid,cintronellal, menthone, and mixtures thereof. In certain embodiments,the turpentine liquid includes at least 60% by volume α-terpineol. Incertain embodiments, the turpentine liquid includes at least 45% byvolume α-terpineol and at least about 15% by volume β-terpineol. Incertain other embodiments, the turpentine liquid includes at least 60%by volume α-terpineol and up to about 30% by volume β-terpineol. Incertain embodiments, between 0.5 and 4 equivalents of the turpentineliquid is used to contact the oil shale and recoverhydrocarbon-containing organic matter. In certain embodiments, between0.5 and 2.0 equivalents of the turpentine liquid is used to contact theoil shale and recover hydrocarbon-containing organic matter.

In another aspect, a system for recovering hydrocarbon-containingorganic material from tar sands is provided. The tar sands recoverysystem includes a tank for supplying a turpentine liquid and acontacting vessel, wherein the contacting vessel includes at least oneinlet for introducing the turpentine liquid and at least one outlet forrecovering an extraction mixture from the contacting vessel. The systemalso includes a first conveyor for supplying tar sands to the contactingvessel. A holding tank that includes a line connecting the holding tankto the contacting vessel is provided, wherein the line connecting thecontacting vessel and the holding tank includes a filter to prevent thepassage of solids to the holding tank. The system also includes a secondconveyor for the recovery and transport of the solids.

In one embodiment, the contacting vessel is a rotary inclined filterthat includes a series of fins or trays for separating and orcontrolling the tar sands. In another embodiment, the fins or trays areprovided to increase or control the contact time between the tar sandsand the turpentine liquid. In certain embodiments, the turpentine liquidcan include α-terpineol. In other embodiments, the turpentine liquid caninclude between about 30% and 70% by volume α-terpineol and betweenabout 25% and 55% by weight β-terpineol.

In another aspect, a system for recovering hydrocarbon-containingorganic matter from oil shale is provided. The system includes a tankfor supplying a turpentine liquid and a grinder for comminuting the oilshale to a reduced particle size. A contacting vessel is provided thatincludes at least one inlet for introducing the turpentine liquid, atleast one inlet for receiving crushed oil shale, at least one outlet forrecovering solids from the contacting vessel and at least one outlet forrecovering an extraction mixture from the contacting vessel. A firstconveyor is provided for supplying crushed oil shale to a contactingvessel. The system further includes a holding tank, wherein the holdingtank includes a line connecting the holding tank to the contactingvessel, wherein the line includes a filter to prevent the passage ofsolids to the holding tank; a second conveyor for recovering solids. Incertain embodiments, the system further includes a line for supplying areaction mixture including recovered hydrocarbons and the turpentineliquid to a refinery for further separation and/or processing. Incertain embodiments, the turpentine liquid can include α-terpineol. Incertain embodiments, the turpentine liquid can include between about 60%and 95% by volume α-terpineol and up to about 30% by weight β-terpineol.In other embodiments, the turpentine liquid can include between about70% and 90% by volume α-terpineol and between about 5% and 25% by weightβ-terpineol.

In another aspect, a system for recovering hydrocarbon-containingorganic matter from coal is provided. The system includes a tank forsupplying a turpentine liquid and a grinder for comminuting coal toproduced particulate matter of a reduced size. A contacting vessel isprovided that includes at least one inlet for introducing the turpentineliquid and at least one outlet for recovering solids and liquids fromthe contacting vessel. The contacting vessel includes also stirringmeans for thoroughly mixing the turpentine liquid and the comminutedcoal. A separator is provided for separating the solids and liquids,wherein the separator includes an inlet, an outlet and a line connectingthe inlet of the separator to the outlet of the contacting vessel. Thesystem also includes a holding tank, wherein the holding tank includes aline that connects the holding tank to the separator, wherein the linecan include a filter to prevent the passage of solids to the holdingtank.

In certain embodiments, the system further includes a filter forselectively preventing particles having a mean diameter greater thanabout 0.85 mm from being introduced to the contacting vessel. In certainother embodiments, the system further includes a line for supplying aliquid coal product to a refinery for further processing. In certainembodiments, the system further includes a first conveyor for supplyingcrushed coal to the contacting vessel. In other embodiments, the systemfurther includes a second conveyor for removing solids from theseparator. In certain embodiments, the turpentine liquid can includeα-terpineol. In embodiments directed to the recovery of hydrocarbonsfrom high grade coal, the turpentine liquid can include between about45% and 80% by volume α-terpineol and between about 15% and 45% byweight β-terpineol. In embodiments directed to the recovery ofhydrocarbons from low grade coal, the turpentine liquid can includebetween about 60% and 95% by volume α-terpineol and between about 0% and30% by weight β-terpineol.

In another aspect, a method for optimizing a turpentine liquid forextraction of hydrocarbon-containing organic matter from hydrocarboncontaining matter is provided. Generally, the method includes providinga sample of the hydrocarbon-containing material and analyzing thehydrocarbon material to determine the type of hydrocarbon beingextracted. A formulation for extraction of hydrocarbon-containingorganic matter from the hydrocarbon material is provided, wherein theformulation is a function of the type of formation and the size of theparticulate hydrocarbon material. Generally, the formulation includes atleast about 40% by volume α-terpineol and at least about 10% by volumeβ-terpineol. The amount of α-terpineol and β-terpineol in theformulation is then adjusted based upon the parameters noted above. Ingeneral, while the above noted method provides a good starting point fordetermining the desired formulation for extraction of varioushydrocarbon containing materials, for other hydrocarbon-containingmaterials and under specified operating conditions, either a series ofstatistically designed experiments or a series of experiments accordingto an optimization method can be performed to determine the optimumcomposition of the liquid turpentine.

As shown in Table 1, the specific formulation for extraction,liquefaction and/or solubilization of hydrocarbon-containing organicmatter from tar sands varies based upon the particle size. In certainembodiments, the method for preparing a turpentine liquid for extractinghydrocarbon-containing organic matter from tar sands includes adjustingthe amount of α-terpineol and β-terpineol in the formulation as afunction of the size of the hydrocarbon rich solid particulate beingextracted. In other embodiments, if the hydrocarbon-containing organicparticulate matter includes low grade coal or an oil shale, the amountα-terpineol in the turpentine liquid is increased and the amount of3-terpineol in the turpentine liquid is decreased. In other embodiments,if the hydrocarbon-containing organic particulate matter includes tarsands, the amount α-terpineol in the turpentine liquid is decreased andthe amount of β-terpineol in the turpentine liquid is increased. Inother embodiments, if the hydrocarbon-containing organic particulatematter includes tar sands and the mean diameter of the particulatematter is less than about 4.76 mm, then the amount α-terpineol in theturpentine liquid is decreased and the amount of β-terpineol in theturpentine liquid is increased. In other embodiments, if thehydrocarbon-containing organic particulate matter includes tar sands andthe mean diameter of the particulate matter is greater than about 1 inch(1 mesh), then the amount α-terpineol in the turpentine liquid isdecreased and the amount of β-terpineol in the turpentine liquid isincreased.

TABLE 1 Formulations for Extraction of Tar Sands based upon ParticleSize Particle Size (Mesh/mm diameter) α-terpineol β-terpineolα-/β-terpene other <4 Mesh (4.76 mm) 30-50% vol 35-55% vol 10% vol 5%vol 1 mesh (1 inch)-4 40-60% vol 30-50% vol 10% vol 5% vol mesh (4.76mm) >1 mesh (1 inch) 50-70% vol 25-45% vol 10% vol 5% vol

Similar to what is shown above with respect to the extraction of tarsands, as shown in Tables 2 and 3, the formulation for extraction,liquefaction and/or solubilization of coal depends both on particle sizeand on the quality of the coal being extracted. In one embodiment of themethod for preparing a turpentine liquid for extractinghydrocarbon-containing organic matter, if the hydrocarbon-containingmatter includes anthracite, bituminous coal, or other high grade coaland the mean diameter of the particulate matter is less than about 0.15mm, then the amount α-terpineol in the turpentine liquid is decreasedand the amount of β-terpineol in the turpentine liquid is increased. Inother embodiments, if the hydrocarbon rich particulate matter includesanthracite, bituminous coal, or other high grade coal and the meandiameter of the particulate matter is greater than about 0.84 mm, thenthe amount α-terpineol in the turpentine liquid is decreased and theamount of β-terpineol in the turpentine liquid is increased. In anotherembodiment, if the hydrocarbon rich particulate matter includes lowgrade coal and the mean diameter of the particulate matter is less thanabout 0.074 mm, then the amount α-terpineol in the turpentine liquid isdecreased and the amount of β-terpineol in the turpentine liquid isincreased. In another embodiment, if the hydrocarbon rich particulatematter includes low grade coal and the mean diameter of the particulatematter is greater than about 0.42 mm, then the amount α-terpineol in theturpentine liquid is decreased and the amount of β-terpineol in theturpentine liquid is increased.

TABLE 2 Formulations for Extraction of High Grade Coal based uponParticle Size Particle Size (Mesh/mm diameter) α-terpineol β-terpineolα-/β-terpene other <100 mesh 45-65% vol 35-45% vol 10% vol 0% vol (0.149mm) 20 mesh 50-70% vol 20-40% vol 10% vol 0% vol (0.841 mm)-100 mesh(0.149 mm) >20 mesh 60-80% vol 15-35% vol 10% vol 0% vol (0.841 mm)

TABLE 3 Formulations for Extraction of Low Grade Coal based uponParticle Size Particle Size (Mesh/mm diameter) α-terpineol β-terpineolα-/β-terpene other <200 mesh 60-80% vol 10-30% vol  5% vol 0% vol (0.074mm) 40 mesh 70-90% vol 5-25% vol 5% vol 0% vol (0.420 mm)-200 mesh(0.074 mm) >40 mesh 75-95% vol 0-20% vol 5% vol 0% vol (0.420 mm)

Similar to what is shown above with respect to the extraction of tarsands, as shown in Table 4, the formulation for extraction, liquefactionand/or solubilization of oil shale depends on particle size. In oneembodiment of the method for preparing a composition for extractinghydrocarbon-containing organic matter, if the hydrocarbon richparticulate matter includes an oil shale and the mean diameter of theparticulate matter is less than about 0.074 mm, then the amountα-terpineol in the turpentine liquid is decreased and the amount ofβ-terpineol in the turpentine liquid is increased. In anotherembodiment, if the hydrocarbon rich particulate matter includes oilshale and the mean diameter of the particulate matter is greater thanabout 0.42 mm, then the amount α-terpineol in the turpentine liquid isdecreased and the amount of β-terpineol in the turpentine liquid isincreased.

TABLE 4 Formulations for Extraction of Oil Shale based upon ParticleSize Particle Size (Mesh/mm diameter) α-terpineol β-terpineolα-/β-terpene other <200 mesh 60-80% vol 10-30% vol  5% vol 0% vol (0.074mm) 40 mesh 70-90% vol 5-25% vol 5% vol 0% vol (0.420 mm)-200 mesh(0.074 mm) >40 mesh 75-95% vol 0-20% vol 5% vol 0% vol (0.420 mm)

The extraction of crude oil similarly depends on the type of crude oilbeing extracted, liquefied, and/or solubilized. As shown in Table 5, theformulation for the extraction, liquefaction and/or solubilization ofcrude oil depends is a function of both particle size and the quality ofthe density of the crude oil being extracted. The method includesproviding a turpentine liquid formulation that includes at least 50% byvolume α-terpineol and at least 20% by volume β-terpineol; adjusting theamount of α-terpineol and β-terpineol in the turpentine liquidformulation based upon the density of the liquid hydrocarbon beingextracted. In one embodiment, if the API gravity of the liquidhydrocarbon being extracted is greater than about 22°, then the amountα-terpineol in the turpentine liquid is decreased and the amount ofβ-terpineol in the turpentine liquid is increased. In anotherembodiment, if the API gravity of the liquid hydrocarbon being extractedis less than about 22, then the amount α-terpineol in the turpentineliquid is increased and the amount of β-terpineol in the turpentineliquid is decreased. As used herein, light oils have an API of at leastabout 31°, medium crude oils have an API of between about 22° and about31°, heavy oil has an API of between about 10° and about 22°, and extraheavy oil has an API of less than about 10°.

TABLE 5 Formulations for Extraction of Crude Oil based upon API DensityCrude Type α-terpineol β-terpineol α-/β-terpene other Light/medium40-70% vol 30-40% vol 10% vol 10% vol crude (API greater than 22°)Heavy/Extra 50-70% vol 20-35% vol 10% vol  5% vol Heavy (API less than22°)

In another aspect, a method for preparing a turpentine liquid forenhancing recovery of liquid hydrocarbon-containing organic matter froma sub-surface formation is provided. The method includes providing aformulation comprising at least 50% by volume α-terpineol and at least20% by volume β-terpineol, and adjusting the amount of α-terpineol andβ-terpineol in the formulation based upon the geological features of thesub-surface formation.

In another aspect, a composition for cleaning and/or recoveringhydrocarbons from a liquid hydrocarbon-containing vessel is provided,wherein the composition includes at least one compound selected fromnatural turpentine, synthetic turpentine, mineral turpentine, pine oil,α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpeneresins, α-terpene, β-terpene, γ-terpene, or mixtures thereof. In otherembodiments, the composition for cleaning and/or recovering hydrocarbonsincludes at least one compound selected from geraniol, 3-carene,dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide,terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In yet otherembodiments, the composition for cleaning and/or recovering hydrocarbonsincludes at least one compound selected from anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof. In one embodiment, the compositionincludes at least one compound from the following: α-pinene, β-pinene,α-terpineol, and β-terpineol. In another embodiment, the compositionincludes at least 25% by volume α-terpineol or p-terpineol.

In another aspect, a method for cleaning and/or recovering hydrocarbonsfrom a liquid hydrocarbon-containing vessel is provided. The methodincludes contacting the interior of vessel with a hydrocarbon cleaningcomposition that includes at least one compound selected from α-pinene,β-pinene, α-terpineol, and β-terpineol to create a mixture: wherein themixture includes the liquid hydrocarbon residue and the hydrocarboncleaning composition. The mixture is recovered and removed from thevessel. In certain embodiments, the cleaning composition includes atleast 25% by volume of α-terpineol or β-terpineol. In certain otherembodiments, the cleaning composition includes at least 25% by volume ofα-terpineol and at least 25% by volume 3-terpineol.

EXAMPLES Example 1

In this example, coal from the Pittsburgh seam in Washington County,Pennsylvania was liquefied with reagent α-terpineol. The coal sample wasobtained from the Coal Bank at Pennsylvania State University, whichprovided the following proximate analyses for it; 2.00 wt. % ofas-received moisture, 9.25 wt. % of dry ash, 38.63 wt. % of dry volatilematter, and 50.12 wt. % of dry fixed carbon. The particle size of coalsample was about 60 mesh. About 60 grams of α-terpineol was gently addedto about 30 grams of the coal sample placed in an extraction vessel,thus giving rise to the reagent-to-sample ratio of 2 to 1. The capped,but not tightly sealed, extraction vessel containing the resultantmixture of α-terpineol and coal was maintained at the constanttemperature of about 96° C. and continually agitated. Without boilingthe α-terpineol, the pressure in the extraction vessel remained at theambient pressure of slightly less than about 1.01×10⁵ Pascals (1 atm).After about 30 minutes, the mixture was filtered and the coal particlesretained on the filter were washed with ethanol and dried to a constantweight. On the basis of weight loss, the conversion, i.e., the extent ofliquefaction, of the coal sample was determined to be about 68 wt. %.

Example 2

This Example is identical to Example 1 in all aspects except two. Aftermaintaining the temperature at about 96° C., for about 30 minutes, asdone in Example 1, the extraction vessel containing the coal sample andα-terpineol was maintained at a temperature at about 135° C. for anadditional period of about 30 minutes. The pressure in the extractionvessel remained at the ambient pressure of slightly less than about1.01×10⁵ Pascals (1 atm). The conversion, i.e., the degree ofliquefaction, of the coal sample was determined to be about 70 wt. %.

Example 3

The coal sample used was from the same source with the same proximateanalyses as those used in the preceding two examples. About 31 grams ofα-terpineol were added to about 31 grams of the coal sample in anextraction vessel. The mixture was maintained at about 96° C. and anambient pressure of slightly less than about 1.01×10⁵ Pascals (1 atm)for about 30 minutes. The conversion, i.e., the degree of liquefaction,of the coal sample attained was determined to be about 71 wt. % byweighing the sample after filtering, washing, and drying as done in thepreceding two examples.

Example 4

This Example is identical to Example 3, except that about 30 wt. % ofα-terpineol was replaced with hexane, providing a reagent that includes70 wt. % α-terpineol and 30 wt. % hexane. This reduced the conversion,i.e., the degree of liquefaction to about 1.3 wt. %.

Example 5

The source and proximate analyses of coal sample and experimentalconditions in terms of temperature, pressure and reagent-to-sample ratiofor this example were the same as those of Example 3. The duration ofthe extraction, however, was reduced from about 30 minutes to about 20minutes. Additionally, about 30 wt. % of the α-terpineol was replacedwith 1-butanol, providing a reagent that includes 70 wt. % α-terpineoland 30 wt. % 1-butanol. The amount of coal liquefied was only about 0.30gram, corresponding to conversion of about 1.0 wt. %.

Example 6

This Example is the same as Example 3 in terms of the source andproximate analyses of coal sample and temperature, pressure and durationof the extraction. The amount of the coal sample used was, however,about 25 grams and the reagent comprised about 24 grams (80 wt. %) ofα-terpineol and about 6 grams (20 wt. %) of xylenes, providing a reagentthat includes 70 wt. % α-terpineol and 30 wt. % xylenes. The coalliquefied was about 10.0 grams, corresponding to conversion of about 40wt. %.

Example 7

In this example, coal from the Wyodak seam in Campbell County, Wyomingwas liquefied with reagent α-terpineol. The coal sample was obtainedfrom the Coal Bank at Pennsylvania State University, which provided thefollowing proximate analyses for it; 26.30 wt. of as-received moisture,7.57 wt. % of dry ash, 44.86 wt. % of dry volatile matter, and 47.57 wt.% of dry fixed carbon. The coal sample's particle size was about 20mesh. About 60 grams of α-terpineol was gently added to about 30 gramsof the coal sample placed in an extraction vessel, a reagent-to-sampleratio of about 2 to 1. The capped, but not tightly sealed, extractionvessel containing the resultant mixture of α-terpineol and coal wasmaintained at a constant temperature of about 96° C. and continuallyagitated. Without boiling of the α-terpineol, the pressure in theextraction vessel remained at the ambient pressure of slightly less thanabout 1.01×10⁵ Pascals (1 atm). After about 30 minutes, the mixture inthe extraction vessel was filtered and the coal particles retained onthe filter were washed with ethanol and dried to a constant weight. Onthe basis of weight loss, the conversion, i.e., the degree ofliquefaction, of the coal sample was determined to be 75 wt. %.

Example 8

The experiment in this example was carried out under the conditionsidentical to those of the preceding example except one. About 15 gramsof α-terpineol were added, instead of about 60 grams, as done in thepreceding example, to about 30 grams of the coal sample, thus attainingthe reagent-to-coal ratio of 0.5 to 1. The conversion, i.e., the degreeof liquefaction, of the coal sample attained decreased from about 75 wt.%, attained in the preceding example, to about 69 wt. %.

Example 9

In this example, about 3 grams of oil shale from the Green-river regionof Colorado was solubilized with about 9 grams of α-terpineol, thusgiving rise to the reagent-to-sample ratio of 3 to 1, to extract kerogen(organic matter) and/or bitumen (organic matter) from it. The organiccarbon content, including both volatile and fixed carbon, was determinedto be about 22.66 wt. % by a certified analysis company. Two experimentswith the oil-shale samples, having the particle size of 60 mesh, werecarried out under the ambient temperature and pressure of about 25° C.and slightly less than about 1.01×10⁵ Pascals (1 atm), respectively. Theweight losses of the samples were determined by weighing afterfiltering, washing with ethanol, and drying. These losses were about 9wt. % after about 30 minutes and about 17 wt. % after about 45 minutes.From these weight losses, the conversion, i.e., the degree of extractionof organic matter, i.e., kerogen and/or bitumen, was estimated to beabout 40 wt. % for the former and was about 75 wt. % for the latter.

Example 10

This Example duplicated the preceding example with the exception that asingle experiment, lasting about 15 minutes, was carried out at thetemperature of about 96° C., instead of about 25° C. The weight loss ofthe oil shale sample was about 12 wt. %, corresponding to theconversion, i.e., the degree of extraction, of kerogen (organic matter)of about 53 wt. %

Example 11

In this example, bitumen (organic matter) in tar sands from Alberta,Canada, was solubilized and extracted with commercial grade syntheticturpentine. The tar-sands sample was obtained from Alberta ResearchCouncil, which provided the following proximate analyses for it; 84.4wt. % of dry solids, 11.6 wt. % of dry bitumen, and 4.0 wt. % ofas-received moisture. About 30 grams of synthetic turpentine were gentlyadded to about 15 grams of the tar-sands sample in a capped, but nottightly sealed, extraction vessel, utilizing a reagent-to-sample ratioof about 2 to 1 by weight. This extraction vessel, containing theresultant mixture of synthetic turpentine and tar sands, was maintainedat a constant temperature of about 96° C. and continually agitated.Without boiling of the synthetic turpentine, the pressure in theextraction vessel remained at the ambient pressure of slightly less thanabout 1.01×10⁵ Pascals (1 atm). After about 20 minutes, the mixture inthe extraction vessel was filtered and the solids (tar sands) retainedon the filter were washed with ethanol and dried to a constant weight.On the basis of weight loss, the conversion, i.e., the degree ofextraction, of bitumen from the tar-sands sample was determined to beabout 100 wt. %.

Example 12

In this example, about 60 grams of the tar-sands sample from the samesource with the same proximate analyses as those of the precedingexample were extracted by about 60 grams of α-terpineol, instead ofcommercial-grade synthetic turpentine, which includes α-terpineol. Theresultant reagent-to-sample ratio was 1 to 1 instead of 2 to 1 as in thepreceding example. The experiment lasted about 30 minutes at thetemperature of about 96° C. under the ambient pressure of slightly lessthan about 1.01×10⁵ Pascals (1 atm). The conversion, i.e., the extent ofextraction, of bitumen (organic matter) in the tar-sands sample wasdetermined to be about 100 wt. %.

Example 13

In this example, about 60 grams of the tar-sands sample from the samesource with the same proximate analyses as those of the preceding twoexamples were extracted by about 60 grams of synthetic turpentine, whichis of the commercial grade. The resultant reagent-to-sample ratio,therefore, was about 1 to 1. The experiment was carried out for about 30minutes at the temperature of about 96° C. under the ambient pressure ofslightly less than about 1.01×10⁵ Pascals (1 atm). The conversion, i.e.,the degree of extraction, of bitumen (organic matter) in the tar-sandssample was determined to be about 70 wt. %.

Example 14

The experiment in this example duplicated that in Example 8 in allaspects except that the reagent-to-sample ratio was reduced from about 2to 1 to about 0.5 to 1: About 60 grams to the tar-sands sample wasextracted by about 30 grams of synthetic turpentine, which is of thecommercial grade. The conversion, i.e., the degree of extraction, ofbitumen (organic matter) decreased from about 100 wt. % attained inExample 9 to about 70 wt. %.

Example 15

The experiment in this example repeated that of the preceding examplewith α-terpineol instead of the commercial-grade synthetic turpentine.The conversion, i.e., the degree of extraction, of bitumen (organicmatter) in the tar-sands sample was about 70 wt. % as in the precedingexample.

Example 16

The experiment in this example was carried out under the ambientpressure of slightly less than about 1.01×10⁵ Pascals (1 atm) with thetar-sands sample from the same source with the same proximate analysesas those in the preceding examples with tar sands. About 60 grams ofcommercial-grade synthetic turpentine was added to about 60 grams of thetar-sands sample, thus giving rise to the reagent-to-sample ratio ofabout 1 to 1. The temperature of the sample and commercial-gradesynthetic turpentine was maintained at about 65° C. for about 30 minutesfollowed by cooling to about 15° C. within about 5 minutes.Subsequently, the tar-sands sample was filtered, washed, dried andweighed. On the basis of weight loss, the conversion, i.e., the degreeof extraction, of bitumen (organic matter) in the tar-sands sample wasdetermined to be about 70 wt. %.

Example 17

The experiment in this example repeated that of the preceding examplewith α-terpineol instead of commercial grade synthetic turpentine. Theconversion, i.e., the degree of extraction, of bitumen (organic matter)increased to about 90 wt. % from about 70 wt. % of the precedingexamples.

Example 18

In this example, a tar-sands sample, weighing about 30 grams, from thesame source with the same proximate analyses as those in Examples 11through 17, was extracted with a liquid that included about 20 grams (80wt. %) of α-terpineol and about 5 grams (20 wt. %) of toluene at thetemperature of about 96° C. under the ambient pressure of slightly lessthan about 1.01×10⁵ Pascals (1 atm). The duration of the experiment(reaction or extraction time) was about 30 minutes. The weigh loss ofthe sample was about 10.2 grams. From this weigh loss, the conversion,i.e., the degree of extraction, of bitumen (organic matter) wasestimated to be about 33 wt. %.

Example 19

Three tar-sands samples, all from the same source with the sameproximate analyses as those used in all preceding examples with tarsands were extracted by reagents comprising various amounts ofα-terpineol and ethanol at the temperature of about 15° C. under theambient pressure of slightly less than about 1.01×10⁵ Pascals (1 atm).The duration of each experiment (reaction or extraction time) was about15 minutes for each tar-sands sample. The first sample was extractedwith a mixture comprising about 0 gram (0 wt. %) of α-terpineol andabout 15 grams (100 wt. %) of ethanol, i.e., with pure ethanol. Thesecond sample was extracted with a mixture comprising about 7.5 grams(50 wt. %) of α-terpineol and about 7.5 grams (50 wt. %) of ethanol. Thethird sample was extracted with a mixture comprising about 12 grams (80wt. %) of α-terpineol and about 3 grams (20 wt. %) of ethanol. Theweight losses and the estimated conversions, i.e., the degrees ofextraction, of bitumen (organic matter) in the three samples were about0.2 gram (1.0 wt. %), 0.6 gram (3.0 wt. %) and 0.9 gram (4.5 wt. %), forthe first, second and third sample, respectively.

Example 20

Irregular-shaped pellets of commercial-grade asphalt whose average sizewas about 15 mm were solubilized and extracted with α-terpineol and atthe ambient temperature of about 22° C. under the ambient pressure ofslightly less than about 1.01×10⁵ Pascals (1 atm). The first sampleweighing about 20 grams was solubilized and extracted with about 40grams of α-terpineol, and the second sample also weighing about 20 gramswas solubilized and extracted with about 20 grams of α-terpineol. Bothsamples were completely dissolved after 30 minutes. These experimentswere carried out to simulate the solubilization and extraction of heavycrude oil, which tends to be rich in asphaltenes like asphalt.

Example 21

In this example, bitumen (organic matter) in tar-sands from the samesource with the same proximate analyses as those used in all previousexamples with tar sands was solubilized and extracted with two varietiesof vegetable oils, soybean oil and corn oil. The vegetable oils arecompletely miscible with turpentine liquid. In the first experiment, atar-sands sample weighing about 15 grams was blended and agitatedcontinually with about 30 grams of soybean oil for about 20 minutes atthe temperature of about 96° C. under the ambient pressure of slightlyless than about 1.01×10⁵ Pascals (1 atm). The weight loss was about 0.5gram from which the conversion, i.e., the degree of extraction, ofbitumen in the sample was estimated to be about 3.3 wt. %. In the secondexperiment, a tar-sands sample weighing about 30 grams was blended andagitated continually with about 60 grams of corn oil for about 30minutes at the temperature of about 175° C. under the ambient pressureof slightly less than about 1.01×10⁵ Pascals (1 atm). The weight losswas about 4.8 grams from which the conversion, i.e., the degree ofextraction, of bitumen in the sample was estimated to be about 12 wt. %.

Example 22

Two tests were performed on Berea sandstone plug core samples todetermine the effect of reagent injection on oil recovery from core. Thefirst test was designed to determine the increment oil recovery due toα-terpineol injection after a field had already undergone waterfloodingto the limit. The selected core contained 9.01 mL of laboratory oilsimulating crude oil. The waterflooding with aqueous solution containing3.0% of potassium chloride produced 4.6 mL of oil. Five (5) pore volumesof α-terpineol injection produced additional 3.61 mL of oil, therebyleaving the core with less than 8.0% of oil remaining in the originalvolume. The second test was designed to represent the increased recoverythat could be expected from a virgin reservoir with α-terpineolinjection. The selected core contained 8.85 mL of laboratory oilsimulating crude oil. Oil production began after approximately 0.5 porevolumes of α-terpineol injection, which was continued until 3.5 porevolumes; however, the majority of the oil was recovered after only 2.5pore volumes of α-terpineol injection. A total of 7.94 mL of laboratoryoil was recovered, thereby leaving the core with less than 7.5% of oilremaining in the original volume.

In one experiment, various different ratios of a turpentine liquid totar sand sample were tested. The turpentine liquid for each of theexperiments provided below had the same formulation, wherein thecomposition included about 60% by volume α-terpineol, about 20% byvolume β-terpineol, and about 20% by volume γ-terpineol. The tar sandswere a different mix of ores from Alberta, Canada, having a bitumencontent of approximately 12% by weight and a water content of betweenabout 4-5% by weight. The experiments were all performed at atmospherictemperature.

As shown in Table 6 below, recovery of hydrocarbons from tar sandsacross all ratios provided below (i.e., ratios of turpentine liquid totar sands ranging from 1:2 to 2:1) resulted in good recovery ofhydrocarbons and little discernible difference. With respect to thetemperature at which the extraction is carried out, it is believed thatthe optimum temperature for the extraction, solubilization and/orliquefaction of hydrocarbons from tar sands is 65° C. As shown in thetable, at about 130° C., the amount of hydrocarbons recovered isreduced. It is noted however, that for certain solids from which it isparticularly difficult to recover hydrocarbons, increasing thetemperature of the extraction solvent can increase the amount ofhydrocarbons that are recovered. Finally, it is shown that exposure timehad very little effect on the amount of materials that were extracted.This is likely because the shortest extraction time was 20 minutes,which is believed to be more than adequate for the extraction of thehydrocarbons from tar sands.

TABLE 6 Weight Ratio of Tar Extractable of tar sand Amount PercentExposure Sand HC extraction to of HC HC Temp, Time, Weight, g weight, gsolvent solvent extracted, g extracted ° C. minutes 15 2.0 30.0 1:2 3.2161 96 20 60 7.8 120.0 1:2 5.4 69 96 30 60 7.8 31.6 2:1 9.6 123 96 30 607.8 60.0 1:1 7.6 97 65 30 60 7.8 60.0 1:1 4.0 51 130 30 60 7.8 60.0 1:16.3 80 65 30

Additional experiments were conducted using alternative solvents, namelyethanol and corn oil, which was compared with the composition thatincluded about 60% by volume α-terpineol, about 20% by volume3-terpineol, and about 20% by volume γ-terpineol. As noted in Table 7provided below, the performance of ethanol and corn oil wereunexpectedly substantially lower than the composition that included 60%by volume α-terpineol, about 20% by volume β-terpineol, and about 20% byvolume γ-terpineol. For example, whereas the terpineol compositionachieved complete or nearly complete extraction of extractablehydrocarbons, ethanol yielded only 10% of the recoverable hydrocarbonsand heated corn oil yielded only 33% of the recoverable hydrocarbons.

TABLE 7 Weight Ratio Tar Extractable of of tar Amount Percent ExposureSand HC extraction sand to of HC HC Temp, Time, Chemical Weight, gweight, g solvent solvent extracted, g extracted ° C. minutes Ethanol 152.0 15.0 1:1 o.2 10 15 15 Corn oil 30 3.9 60.0 2:1 1.3 33 175 3060/20/20 60 7.8 60.0 1:1 7.6 97 65 30 terpineol 60/20/20 60 7.8 31.6 2:19.6 123 96 30 terpineol

As shown in Table 8 below, the performance of various turpentine liquidformulations, including turpentine liquid formulations that include onlyα-terpineol and α-terpineol in combination with various known organicsolvents, are provided. The first three compositions presented in thetable include α-terpineol, β-terpineol, and γ-terpineol. For example,the first same includes about 60% by volume α-terpineol, about 30% byvolume β-terpineol, and about 10% by volume γ-terpineol. The resultsunexpectedly show that as the concentration of the α-terpineolincreases, performance of the turpentine liquid increases to the pointthat when the turpentine liquid includes approximately 70% α-terpineol,full extraction of the hydrocarbon material from the tar sand sample isachieved.

The second set of data is presented for extraction of hydrocarbonbearing tar sands with pure α-terpineol. As shown, extraction of greaterthan 100% is achieved, likely due to inconsistencies in the hydrocarboncontent of the samples. However, the results generally demonstrate theunexpected result that α-terpineol is capable of extractingsubstantially all of the recoverable hydrocarbon from a tar sand sample.

Finally, the last data provided in Table 8 illustrates the effectivenessof mixed systems of α-terpineol and known organic solvents. As shown,substantially complete recovery of recoverable hydrocarbons is achievedwith a composition that includes a 1:1 ratio of α-terpineol to ethanol.This is unexpected as pure ethanol only removed about 10% of the totalrecoverable hydrocarbons. Additionally, mixed systems that includeeither a 1:1 or a 3:1 ratio of α-terpineol to toluene still resulted inthe recovery of 77% and 92% of the total recoverable hydrocarbons. Thiswas an unexpected result.

TABLE 8 Tar Ratio of Amount Percent Exposure Chemical Sand ExtractableWt. of tar sand of HC HC Temp, Time, comp. wt., g HC wt., g solvent tosolvent extracted, g extracted ° C. minutes 60/30/10 60 2.0 60.0 1:1 7.191 96 30 terpineol 40/30/20 60 7.8 60.0 1:1 4.7 60 96 30 terpineol70/20/10 60 7.8 60.0 1:1 7.9 101 96 30 terpineol 100/0/0 60 7.8 60.0 1:110.0 128 96 30 terpineol 100/0/0 60 7.8 120.0 1:2 8.7 111 96 30terpineol 100/0/0 60 7.8 31.0 2:1 9.6 123 96 30 terpineol 50% α- 15 2.015.0 1:1 8.1 103 65 30 terpineol/ 50% ethanol 80% α- 15 2.0 15.0 1:1 1.262 15 15 terpineol/ 20% ethanol 75% α- 30 3.9 25.0   1:0.8 1.8 92 15 15terpineol/ 25% toluene 50% α- 30 3.9 26.0   1:0.9 3.0 77 96 30terpineol/ 50% toluene 50% α- 30 3.9 26.0   1:0.9 2.4 61 96 30terpineol/ 50% xylenes

The results for the extraction of hydrocarbon-containing organic matterfrom hydrocarbon-containing material described in the specification, andespecially in the Examples above, were unexpected.

As used herein, the terms first, second, third and the like should beinterpreted to uniquely identify elements and do not imply or restrictto any particular sequencing of elements or steps.

As used herein, the terms about and approximately should be interpretedto include any values which are within 5% of the recited value.Furthermore, recitation of the term about and approximately with respectto a range of values should be interpreted to include both the upper andlower end of the recited range. As used herein, the terms first, second,third and the like should be interpreted to uniquely identify elementsand do not imply or restrict to any particular sequencing of elements orsteps.

While the invention has been shown or described in only some of itsembodiments, it should be apparent to those skilled in the art that itis not so limited, but is susceptible to various changes withoutdeparting from the scope of the invention.

The invention claimed is:
 1. A method of extractinghydrocarbon-containing organic matter from a hydrocarbon-containingmaterial using a homogenous one-phase hydrocarbon-extracting liquidconsisting essentially of a turpentine liquid, comprising the steps of:contacting the hydrocarbon-containing material with a homogenousone-phase hydrocarbon-extracting liquid consisting essentially of aturpentine liquid to form a homogeneous one-phase extraction mixture anda residual material, the homogeneous one-phase extraction mixturecomprising at least a portion of the hydrocarbon-containing organicmatter extracted into the turpentine liquid, the residual materialcomprising at least a portion of non-soluble material from thehydrocarbon-containing material that are not soluble in the turpentineliquid; separating the extraction mixture from the residual material;and separating the extraction mixture into a first portion and a secondportion, the first portion of the extraction mixture comprising ahydrocarbon product stream comprising at least a portion of thehydrocarbon-containing organic matter, the second portion of theextraction mixture comprising at least a portion of the turpentineliquid.
 2. The method of claim 1, wherein said turpentine liquid isselected from the group consisting of natural turpentine, syntheticturpentine, mineral turpentine, pine oil, α-pinene, β-pinene,α-terpineol, β-terpineol, γ-terpineol, terpene resins, α-terpene,β-terpene, γ-terpene, and mixtures thereof.
 3. The method of claim 1,wherein said turpentine liquid is selected from the group consisting ofgeraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane,2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,isoborneol, p-menthan-8-ol, α-terpinyl acetate, citronellol,p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, andmixtures thereof.
 4. The method of claim 1, wherein said turpentineliquid is selected from the group consisting of anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.
 5. The method of claim 1, wherein saidhydrocarbon-containing organic matter is solid or semi-solid, whereinsaid hydrocarbon-containing material comprises a plurality of particles,the particles having an average particle diameter.
 6. The method ofclaim 5, wherein the average particle diameter is from about 0.74millimeters to about 25 millimeters.
 7. The method of claim 1, furthercomprising the step of contacting the hydrocarbon-containing materialwith a second liquid selected from the group consisting of loweraliphatic alcohols, lower alkanes, lower aromatics, aliphatic amines,aromatic amines, and mixtures thereof.
 8. The method of claim 7, whereinsaid second liquid is selected from the group consisting of ethanol,propanol, isopropanol, butanol, pentane, heptane, hexane, benzene,toluene, xylene, anathracene, tetraline, triethylamine, aniline, andmixtures thereof.
 9. The method of claim 8, wherein the step ofcontacting the hydrocarbon-containing material with said turpentineliquid further the step of agitating said reaction mixture using waterat a temperature around a boiling point of water as an agitant.
 10. Themethod of claim 1 further comprising the step of heating the turpentineliquid to a temperature to a point above ambient temperature to about200° C. before contacting the turpentine liquid with thehydrocarbon-containing material.
 11. The method of claim 1, wherein saidhydrocarbon-containing material and said turpentine liquid are contactedat a pressure of from about 1.0×10⁴ Pascals (0.1 atm) to about 5.0×10⁶Pascals (50.0 atm).
 12. The method of claim 1, further comprisingsupplying at least a portion of the second portion of the extractionmixture to the contacting step.
 13. The method of claim 1, furthercomprising the step of providing means for contacting saidhydrocarbon-containing organic matter and said turpentine liquid in situin an underground formation containing said hydrocarbon-containingorganic matter, and means for extracting said hydrocarbon-containingorganic matter from said underground formation.
 14. The method of claim1, wherein said hydrocarbon containing material is contacted by saidturpentine liquid at a temperature of less than about 300° C.
 15. Themethod of claim 1, wherein the hydrocarbon-containing material iscontacted by said turpentine liquid at a temperature of less than about60° C.
 16. The method of claim 1 wherein the hydrocarbon-containingmaterial is in an underground formation and the contacting of thehydrocarbon-containing material with said turpentine liquid occurs insitu in the underground formation; and further comprising the step ofrecovering the extraction mixture through a production well in fluidcommunication with the underground formation, wherein the residualmaterial remains in situ in the underground formation.
 17. The method ofclaim 16 further comprising the step of reinjecting the recycle streaminto the injection well for further extraction of hydrocarbon material.18. The method of claim 16 wherein the underground formation isundergoing primary recovery of the hydrocarbon material.
 19. The methodof claim 1 wherein the turpentine liquid comprises at least about 30% byvolume α-terpineol and at least about 15% β-terpineol.
 20. The method ofclaim 1 wherein the turpentine liquid comprises between about 50% byvolume α-terpineol and at least about 20% by volume β-terpineol.
 21. Themethod of claim 1 wherein the turpentine further comprises at least oneof α-terpene, β-terpene or γ-terpene.
 22. The method of claim 1 whereinthe turpentine liquid comprises α-terpineol and β-terpineol, wherein theratio of α-terpineol to β-terpineol is at least about 1.3:1.
 23. Themethod of claim 1 wherein the turpentine liquid comprises α-terpineoland β-terpineol, wherein the ratio of α-terpineol to β-terpineol is atleast about 2:1.
 24. The method of claim 1 for extractinghydrocarbon-containing organic matter from a hydrocarbon-containingmaterial, said hydrocarbon material comprising tar sands, wherein thecontacting of the hydrocarbon-containing material with said turpentineliquid comprises the step of supplying the tar sands to an interiorportion of an extraction vessel and supplying the turpentine liquid tothe interior portion of the extraction vessel for a period of timeoperable to extract a substantial portion of the hydrocarbon-containingorganic matter from the hydrocarbon-containing material.
 25. The methodof claim 1 for extracting hydrocarbon-containing organic matter from ahydrocarbon-containing material, said hydrocarbon material comprisingoil shale, the method further comprising the steps of: grinding thehydrocarbon-containing organic matter to create a plurality ofparticles, the particles defining an average diameter size in the rangeof 4.8 mm to 25 mm such that the plurality of particles is contactingthe turpentine liquid.
 26. The method of claim 1 for extractinghydrocarbon-containing organic matter from a hydrocarbon-containingmaterial, said hydrocarbon material comprising coal, the method furthercomprising the steps of: grinding the hydrocarbon-containing organicmatter to create a plurality of particles, the particles defining anaverage diameter size in the range of 0.8 mm to 0.07 mm such that theplurality of particles is contacting the turpentine liquid.
 27. A methodof extracting hydrocarbon-containing organic matter from ahydrocarbon-containing material selected from coal, oil shale, tarsands, crude oil, heavy crude oil, natural gas, or a combinationthereof, the method comprising the steps of: contacting thehydrocarbon-containing material with α-terpineol such that an extractionmixture is formed and a residual material is formed, the extractionmixture comprising at least a portion of the hydrocarbon-containingorganic matter extracted into said α-terpineol, the residual materialcomprising at least a portion of non-soluble material from thehydrocarbon-containing material that are not soluble in the α-terpineol;and separating the extraction mixture from the residual material. 28.The method of claim 27 further comprising the step of separating theextraction mixture into a hydrocarbon product stream and a recyclestream, the hydrocarbon product stream comprising at least a portion ofthe hydrocarbon-containing organic matter, the recycle stream containingat least a portion of the α-terpineol.
 29. The method of claim 28further comprising the step of recycling the recycle stream to contactthe hydrocarbon-carbon containing material.
 30. A method for recoveringhydrocarbon-containing organic matter from tar sands, the methodcomprising: obtaining a tar sand sample comprising recoverablehydrocarbon-containing organic matter; supplying the tar sand sample toa contacting vessel, said contacting vessel comprising at least oneinlet for supplying the turpentine liquid; contacting the tar sandsample with a homogenous one-phase hydrocarbon-extracting liquidconsisting essentially of α-terpineol and β-terpineol in a contactingvessel and agitating the tar sand sample with the hydrocarbon-extractingliquid to form a homogeneous one-phase extraction mixture and a residualmaterial, the extraction mixture comprising at least a portion of thehydrocarbon-containing organic matter extracted into thehydrocarbon-extracting liquid, the residual material comprising at leasta portion of non-soluble material from the tar tar sand sample that isnot soluble in the hydrocarbon-extracting liquid, said contacting vesselcomprising at least one inlet for supplying a hydrocarbon-extractingliquid; separating the extraction mixture from the residual material;separating the extraction mixture into a hydrocarbon product stream anda hydrocarbon-extracting liquid recycle stream, the hydrocarbon productstream comprising at least a portion of the hydrocarbon-containingorganic matter from the tar tar sand sample; and recycling at least aportion of the hydrocarbon-extracting liquid recycle stream to thecontacting step.
 31. A method for recovering hydrocarbon-containingorganic matter from comminuted hydrocarbon-containing oil shale, themethod comprising: providing the comminuted hydrocarbon-containing oilshale; providing a first liquid consisting essentially of a turpentineliquid; filtering the comminuted hydrocarbon-containing oil shale;feeding the crushed hydrocarbon-containing oil shale to a contactingvessel, the contacting vessel comprising at least one inlet forsupplying the turpentine liquid to the contacting vessel; contacting thecomminuted hydrocarbon-containing oil shale with turpentine liquid toform a homogenous one-phase extraction mixture and a residual materialis formed, the extraction mixture comprising at least a portion of thehydrocarbon-containing organic matter and the turpentine liquid, theresidual material comprising at least a portion of non-soluble materialfrom the oil shale that is not soluble in the turpentine liquidseparating the extraction mixture from the residual material; andseparating the hydrocarbon-containing organic matter from the turpentineliquid in the extraction mixture to produce a hydrocarbon product streamand a turpentine liquid recycle stream, the hydrocarbon product streamcomprising at least a portion of the hydrocarbon-containing organicmatter from the comminuted hydrocarbon containing oil shale; andrecycling at least a portion of the turpentine liquid recycle stream tothe contacting step.
 32. A method for recovering hydrocarbon-containingorganic matter from hydrocarbon-containing coal rich sub-surfaceformation, the method comprising: obtaining coal, said coal comprising arecoverable hydrocarbon-containing organic matter; grinding the coal toproduce crushed coal; filtering the crushed coal; feeding the crushedcoal to a contacting vessel, said contacting vessel comprising at leastone inlet for supplying a turpentine liquid consisting essentially ofturpentine to the contacting vessel; contacting the crushed coal withturpentine liquid to form a homogenous one-phase extraction mixture anda residual material is formed, the extraction mixture comprising atleast a portion of the hydrocarbon-containing organic matter and theturpentine liquid, the residual material comprising at least a portionof non-soluble material from the coal that is not soluble in theturpentine liquids; separating the residual material from the extractionmixture; and separating the hydrocarbon-containing organic matter fromthe turpentine liquid to produce a hydrocarbon product stream and aturpentine liquid recycle stream, the hydrocarbon product streamcomprising at least a portion of the hydrocarbon-containing organicmatter from the coal; and recycling at least a portion of the turpentineliquid recycle stream to the contacting step.
 33. A method forincreasing recovery of hydrocarbon-containing organic matter from aproduction well coupled to a hydrocarbon-containing sub-surfaceformation, the subsurface formation comprising hydrocarbon-containingmaterial, the method comprising: providing an injection well, saidinjection being in fluid communication with the sub-surface formation;providing a first liquid, the first liquid consisting essentially of aturpentine liquid comprising terpineol; injecting the turpentine liquidthrough the injection well and into the formation, wherein theturpentine liquid and the hydrocarbon-containing organic matter from thehydrocarbon containing sub-surface formation form a homogenous one-phaseextraction mixture comprising at least a portion of the extractionmixture hydrocarbon-containing organic matter and at least a portion ofthe turpentine liquid; recovering the extraction mixture from theformation through the production well; and separating the extractionmixture to produce a hydrocarbon product stream and a turpentine liquidstream.
 34. In a method of extracting hydrocarbon-containing organicmatter from a hydrocarbon-containing material utilizing surfactantaddition to the hydrocarbon-containing material, the method comprisingthe method of claim 1, wherein said extracting occurs only after anysurfactant addition to said organic matter.
 35. The method of claim 1,wherein said hydrocarbon-containing material is contacted with at least0.5 pore volume of turpentine liquid.
 36. The method of claim 1, whereinsaid hydrocarbon-extracting liquid is α-terpineol or syntheticturpentine.
 37. The method of claim 1, wherein saidhydrocarbon-extracting liquid contains no water.
 38. The method of claim1, wherein said hydrocarbon-extracting liquid that contacts saidhydrocarbon-containing material contains at least about 70% of saidturpentine liquid.
 39. The method of claim 1, further comprising thestep of agitating said extraction mixture during said contacting step.40. The method of claim 1, further comprising the step of contactingsaid hydrocarbon-containing material with a turpentine-miscible secondliquid wherein the ratio of said turpentine liquid to saidturpentine-miscible liquid is greater than or equal to 1:1.
 41. Themethod of claim 1, further comprising contacting saidhydrocarbon-containing material with a turpentine-miscible solvent.